Environmental Monitoring: Where

will technology be in 10 years?

Paul Winkler

AB SCIEX

2 © 2013 AB SCIEX

Things you should know

The discussion will be about LC/MS

for environmental applications (no omics)

These are my musings, not official

AB Sciex statements

This is intended to be a technology talk, not a

vendor talk

The historical discussion is a broad swipe

and any omission is not intentional

3 © 2013 AB SCIEX

Outline

Historical Evolution of LC/MS

Current technology and areas for

improvement

Where will be in the future?

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Historical evolution of LC/MS

1968 – Direct Liquid Injection (Tal’roze)

–Not suitable to reverse phase

–Low sensitivity and reliability

1975 – Atmospheric Pressure Chemical

Ionization (Horning)

1976 – Moving Belt (McFadden)

–First interface to provide EI spectra

–Mechanically complex, memory effects

and poor reverse phase performance

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Historical evolution of LC/MS

1978 – Thermospray (Vestal)

– Operated with reverse phase chromatography

– Poor stability but adequate sensitivity

1982 – Atmopspheric Pressure Chemical Ionization

(Henion)

– Good perfomrance with reverse phase separations

– Good sensitivity

1984 – Electrospray (Fenn)

– Superior sensitivity and stability

– Good performance with reverse phase solvents

– Wide compound application

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Historical evolution of mass spectrometry

1934 – Double focusing magnetic sector

1953 – Quadrupole (Paul)

1956 – GC/MS (McLafferty)

1978 – Triple quadrupole MS (Yost)

1984 – QTOF (Glish)

2000 – Orbitrap

2003 – Qtrap (Hager)

2004 – Differential mobility spectrometry

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The last 20 years

1993 – Ion Spray

– Thermospray

– Particle Beam

– Single quadrupole and triple quadrupole instruments

– Sensitivity in the low PPM range

– Poor operational stability

– Environmental applications just beginning to be

developed

– Selectivity limitations require significant cleanup

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The last 20 years

2013 – Electrospray

– APCI

– Triple quadrupoles, Qtraps, Orbitraps and QTOFs

– Improved selectivity with MRMn, differential mobility

– Sensitivity in the low PPT range

– Very stable operational stability

– Better instrumentation for compound identification and

confirmation

– Several environmental applications – flame retardants,

pesticides, PPCP, explosives, perchorate, UMCR….

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0.0

20.0

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Ion suppression vs. dilution

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Ion suppression vs. dilution

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Ion suppression vs. dilution

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Ion suppression vs. dilution

The Next Ten years?

Methamidophos

(RT = 2.1 min)

Acetamiprid

(RT = 6.2 min)

50x dilution needed

50x dilution needed

200x dilution needed

Carbaryl

(RT = 7.5 min)

100x dilution needed

Bromuconazole

(RT = 12.9 min)

10 © 2013 AB SCIEX

The next 10 years?

Matrix Interference with Electrospray

–Expect to see electrospray sources that exhibit

significantly less ionization suppression

–Especially important for environmental

applications as this will allow direct injection

analyses and easier soil extractions

11 © 2013 AB SCIEX

The next 10 years?

Improvements to APCI sources

Relative Sensitivities of ESI and APCI to

31 Pharmaceutical Compound Test Suite

ESI ≤ APCI 8 Compounds 25%

APCI 5 to 20x lower than

ESI

10 Compounds 32%

APCI 20 to 100x

lower than ESI

2 Compounds 6%

APCI > 100x

lower than ESI

11 Compounds 35%

12 © 2013 AB SCIEX

The next 10 years?

APCI source improvements

–Better source design to improve transmission of

ions from the source region to the mass spec

– Inherent freedom from APCI will drive an

increase in these methods in environmental

analyses

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The next 10 years?

XIC of ± 19mDa (100ppm)

S/N ~ 20

XIC of ± 1.9mDa (10ppm)

S/N ~ 40

XIC of ± 190mDa (1000ppm)

S/N ~ 4

10 μg/kg Carbendazim in feed

after 20x dilution

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The next 10 years?

Selectivity

– Improvements in resolution for QTOF type

instruments with less loss of sensitivity

–Operational resolution of QTOFs in the range of

100,000

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MRM

276-203

MRM

276-168

MRM

276-132

The next 10 years?

Detection on QTRAP® 5500 with SelexION™ (top: no DMS, bottom: DMS with IPA)

16 © 2013 AB SCIEX

The next 10 years?

Selectivity

– Improved transmission for differential mobility

devices

–Differential mobility will be especially important

for environmental applications as this will

radically reduce the demands of sample

preparation

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The next 10 years?

Compound Identity/Confirmation

Dicloran

Omethoate

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The next 10 years?

Improvements to collision processes to increase the

information content in MS/MS spectra

Need to identify detections with more certainty as

environmental LC/MS applications increase

Reliance on MRM ratios will not be sufficient information

for compound confirmation. Will require full scan MS/MS

Will need accompanying increase in scan speed to obtain

data for 3-6 second wide peaks

19 © 2013 AB SCIEX

The future of environmental analyses In

cre

asin

g M

W

Increasing polarity

Other chemical

properties of interest:

- Solubility

- Structure

- Stability

- Charge

Quaternary

ammonium salts

Acidic/polar herbicides

Macrolide

antibiotics

Acrylamide

Melamine

Packaging migrants

Mycotoxins

Marine biotoxins

Assorted pesticides

Heterocyclic antibiotics

Aminoglycoside

antibiotics

Assorted

antibiotics

20 © 2013 AB SCIEX

Other contaminants emerge almost daily In

cre

asin

g M

W

Increasing polarity

Quaternary

ammonium salts

Acidic/polar herbicides

Macrolide

antibiotics

Acrylamide

Melamine

Packaging migrants

Mycotoxins

Marine biotoxins

Assorted pesticides

Heterocyclic antibiotics

Aminoglycoside

antibiotics

Assorted

antibiotics

Assorted

pesticide

metabolites Other unknown

adulterants / chemical

contaminants

Allergens

Steroids &

Hormones

‘Gutter oil’

Recycled chemical

migrants

21 © 2013 AB SCIEX

Ten years from now:

Decrease in matrix interference will make LC/MS the

method of choice for a large section of environmental

analyses

Applications will include possibly an equal mix of APCI or

ESI methods

Compound confirmation in LC/MS analyses will be similar

to TIC’s from GC/MS today but with a much wider

compound range

Data that is obtained will have comprehensive catalogue

of all chemicals present allowing retrospective review

22 © 2013 AB SCIEX

Thank you for listening !